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71.
We report the first observation of 77Se nuclear magnetic resonance (NMR) in octaneselenol-protected Au nanoparticles of an average particle size of 2.5 nm. The 77Se NMR characteristics observed, i.e., broad line shape, fast nuclear spin-lattice, and spin-spin relaxation rates, which are reminiscent of 13C NMR of CO on transition metal surfaces, strongly suggest that Se becomes metallic upon binding to the Au nanoparticle surfaces. 相似文献
72.
Gaul C Njardarson JT Shan D Dorn DC Wu KD Tong WP Huang XY Moore MA Danishefsky SJ 《Journal of the American Chemical Society》2004,126(36):11326-11337
The first asymmetric total synthesis of (+)-migrastatin (1), a macrolide natural product with anti-metastatic properties, has been accomplished. Our concise and flexible approach utilized a Lewis acid-catalyzed diene aldehyde condensation (LACDAC) to install the three contiguous stereocenters and the trisubstituted (Z)-alkene of migrastatin (2 + 3 --> 21). Construction of the two remaining stereocenters and incorporation of the glutarimide-containing side chain was achieved by an anti-selective aldol addition of propionyl oxazolidinone 28 to angelic aldehyde 27, followed by a Horner-Wadsworth-Emmons (HWE) coupling of 32 with glutarimide aldehyde 5. Finally, the assembly of the macrocycle was realized by a highly (E)-selective ring-closing metathesis (35 --> 37). Utilizing the power of diverted total synthesis (DTS), a series of otherwise inaccessible analogues was prepared and evaluated for their potential as tumor cell migration inhibitors in several in vitro assays. These studies revealed a dramatic increase in activity when the natural motif was considerably simplified, presenting macrolactones 45 and 48, as well as macrolactam 55, macroketone 60, and CF(3)-alcohol 71 as promising anti-metastatic agents. 相似文献
73.
Metathesis reactions between Ru(2)(DMBA)(4)Cl(2) (DMBA = N,N'-dimethylbenzamidinate) and MX (M = Na and K) yielded bis-adduct derivatives Ru(2)(DMBA)(4)X(2) (X = CN (1), N(3) (2), N(CN)(2) (3)). Metathesis reactions between Ru(2)(DMBA)(4)(NO(3))(2) and KI resulted in Ru(2)(DMBA)(4)I(2) (4). Compound 1 is diamagnetic, while compounds 2-4 are paramagnetic (S = 1). Both compounds 1 and 2 undergo two reversible one-electron processes, an oxidation and a reduction, while compound 3 features a quasireversible reduction. Single-crystal X-ray diffraction studies revealed that the Ru-Ru bond lengths are 2.4508(9), 2.3166(7), 2.304[1], and 2.328(1) A for compounds 1-4, respectively. Structural and electrochemical data clearly indicate that the axial ligands impart a significant influence on the electronic structures of diruthenium species. 相似文献
74.
Ming‐Liang Tong Wei Li Xiao‐Ming Chen Shao‐Liang Zheng Seik Weng Ng 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m232-m234
The title compound, [Cu2(C2H3O2)4(C11H9N)2] or [Cu2(MeCO2)4(phpy)2] (phpy is 4‐phenylpyridine), consists of centrosymmetric dimers in which the CuII atoms display a square‐pyramidal CuO4N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions. 相似文献
75.
S. N. Tong Kyung Y. Park H. James Harwood 《Journal of polymer science. Part A, Polymer chemistry》1984,22(5):1097-1113
Model p-cresol-formaldehyde condensates having regular sequences of methylene ether and methylene linkages were prepared by the self-condensation of dimethylol derivatives of p-cresol-formaldehyde condensates (2-hydroxy-5-methyl-1,3-benzenedimethanol, 3,3′-methylene-bis[2-hydroxy-5-methylbenzenemethanol] and 3,3′-[(2-hydroxy-5-methyl-m-phenylene)dimethylene]-bis[2-hydroxy-5-methylbenzenemethanol]). 300-MHz 1H-NMR spectra of these polymers and of their acylated derivatives were recorded and used to develop resonance assignments for the various types of protons present in these polymers. The spectra were found to be sensitive to end-group and sequence distribution effects. 相似文献
76.
Amphiphilic biodegradable poly(CL-b-PEG-b-CL) triblock copolymers have been successfully prepared by the ring-opening polymerization of ε-caprolactone (CL) employing yttrium tris(2,6-di-tert-butyl-4-methylphenolate) [Y(DBMP)3] as catalyst and double-hydroxyl capped PEGs (DHPEG) as macro-initiator. The triblock architecture, molecular weight, thermal and crystallization properties of the copolymers were characterized by NMR spectra, SEC, DSC and WAXD analyses. The isothermal crystallization behavior of the copolymers was investigated by POM analysis in detail, which is greatly influenced by the length of PCL and PEG blocks. On the POM micrograph of PEG10,000-(PCL8600)2, a unique morphology of concentric spherulites was observed due to the sequent crystallization of the PCL and PEG blocks. 相似文献
77.
Aiming at distinguishing between the sedimentary environments in shallow sea using elemental geochemical markers, the determinations of trace elements in carbonate rocks by thermal neutron, epithermal neutron and short-irradiation activation analysis have been studied, and more than 30 major and trace elements determined. Al, Cl, Sc, Ti, V, Cr, Fe, Co, As, Br, Rb, Sb, Cs, Lu, Hf, Ta, Th and U were found to be the effective distinguishing markers for the secondary environments in shallow sea. 相似文献
78.
Synthesis of new tetrazene(N-N=N-N)-linked bi(1,2,4-triazole) 总被引:2,自引:0,他引:2
Sheng Hua Li Si Ping Pang Xiao Tong Li Yong Zhong Yu Xin Qi Zhao 《中国化学快报》2007,18(10):1176-1178
The reaction of 4-amino-1,2,4-triazole with sodium dichloroisocyanurate (SDCI) afforded new tetrazene(N-N=N-N)-linked bi(1.2,4-triazole) 2a in excellent yield.Increasing the molar ratio of SDCI to 4-amino-1,2,4-triazole,the chlorinated product 1,5,5′- trichloro-4,4′-azo-1,2,4-triazole (2b) was formed.These new compounds have been characterized by MS,~1H NMR,~(13)C NMR,and elemental analysis. 相似文献
79.
80.
[reaction: see text] Effective epoxidation of lipophilic alkenes using hydrogen peroxide was accomplished with the manganese sulfate/bicarbonate catalytic system in an ionic liquid at room temperature. 相似文献